CN101203298A - Multicolor-encoded colloidal particles coated with metal nanoparticles mixture having colors in the visible region and method for preparing the same - Google Patents

Multicolor-encoded colloidal particles coated with metal nanoparticles mixture having colors in the visible region and method for preparing the same Download PDF

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Publication number
CN101203298A
CN101203298A CNA2006800179087A CN200680017908A CN101203298A CN 101203298 A CN101203298 A CN 101203298A CN A2006800179087 A CNA2006800179087 A CN A2006800179087A CN 200680017908 A CN200680017908 A CN 200680017908A CN 101203298 A CN101203298 A CN 101203298A
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metal
particle
colloidal
metal nanoparticle
metal nanoparticles
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CN101203298B (en
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郑峰贤
林勇泰
金真庆
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Korea Research Institute of Bioscience and Biotechnology KRIBB
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Korea Research Institute of Bioscience and Biotechnology KRIBB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0086—Processes carried out with a view to control or to change the pH-value; Applications of buffer salts; Neutralisation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0549—Hollow particles, including tubes and shells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Abstract

The present invention relates to multicolor colloidal particles coated with a metal nanoparticle mixture having colors in the visible region and a method for preparing the same. In particular, relates to a metal nanoparticle mixture in which two or more nanoparticles selected from the group consisting of metal nanoparticles exhibiting red color; metal nanoparticles exhibiting yellow color; and metal nanoparticles exhibiting blue color, are mixed in various compositional ratio, multicolor colloidal particles in which polymer or mineral colloidal particles are coated with the metal nanoparticle mixture, and a method for preparing the same. According to the present invention, all colors that are in the visible region can be developed by suitably mixing metal nanoparticles exhibiting three colors, and multicolor colloidal particles can be prepared by coating polymer or mineral colloidal particles with a metal nanoparticle mixture exhibiting various colors.

Description

Scribble polychrome-coding colloidal particle of the metal nanoparticles mixture with color in the visible range and preparation method thereof
Technical field
The present invention relates to scribble colloidal particle that shows the metal nanoparticles mixture of color in the visible range and preparation method thereof.Particularly, the present invention relates to show the metal nanoparticles mixture of visible range color, wherein two or more nano particle is selected from by showing red metal nanoparticle, show yellow metal nanoparticle and showing the group that blue metal nanoparticle is formed, and these nano particles mix with multiple composition ratio.The invention still further relates to the polychrome colloidal particle that on polymer or colloidal inorganic particle, scribbles metal nanoparticles mixture, and preparation method thereof.
Background technology
Nano particle is made up of gold and silver, and it has the phenomenon (surface plasmon resonance effect) of strong absorption or scattering special wavelength light.Because this effect, metal nanoparticle has been used to show versicolor pigment.Compare with organic dyestuff, metal nanoparticle has outstanding absorption and scattering properties and optical stability.In addition, the surface plasmon resonance frequency can be by changing its size, and shape, structure wait to be controlled, thereby prepares the metal nanoparticle that can show multiple color.
By utilizing the characteristic of above-mentioned metal nanoparticle, Study on Biosensor is actively developed, this biology sensor can the detection of biological material for example, gene (DNA) or protein, this be because look become needn't be with special optical device or instrument and as long as just can be easy to observe by naked eyes.
Although metal nanoparticle is used as its essential form of colloidal solution, yet can be after scribbling these metal nanoparticles on the matrix as the instrument that improves surface-enhanced raman scattering (SERS) effect, or by with it with the uniform array form or it is coated on the sphero-colloid particle surface is used as the biological and chemical sensor.
Based on these reasons, up to date, by the size and the shape of control metal nanoparticle, many researchs of the nano particle of the multiple color of preparation demonstration are actively developed.Publication number is that 2005/0287680 United States Patent (USP) has disclosed to use and shows multiple color metal nanoparticle and the method for detection of biological sample according to size.
Yet, use the conventional system preparation to scribble the colloidal particle of the metal nanoparticles mixture that shows multiple color, size need prepare respectively under different reaction conditions with polytype particle that shape differs from one another, and also will be difficult to reproducibly show multiple color.
Therebetween, publication number is that the Korean Patent of 10-2005-0030398 has disclosed to contain and can effectively suppress because sebum secretion and the artificial cosmetic composition of luminous gold silicon (gold silica) nano particle.Yet used golden nanometer particle is confined to show the red 20-50nm particle that is, and it also is difficult to show multiple color.In addition, publication number is that 2004/0058488 United States Patent (USP) has disclosed and uses colloidal particle to detect the method for chemistry, biology and biochemical samples as sensor, and this colloidal particle has number of chemical functional group in its surface.Yet because this method makes with light tweezer (optical tweezers) test sample, its test sample is not easy very much.
The applicant has carried out many researchs to address the above problem, and final discovery is passed through with suitable composition ratio synthesis display redness, three kinds of yellow and blue metal nanoparticles can prepare the polychrome colloidal particle that shows multiple color, thereby have finished the present invention.
Summary of the invention
Correspondingly, the present invention has finished and has solved the existing in prior technology problem, and one object of the present invention is, a kind of metal nanoparticles mixture is provided, by comprehensive two or more metal nanoparticle, it can show the multiple color in the visible range.
Another object of the present invention is, the multi-colour metal colloidal particle is provided, and wherein metal nanoparticles mixture is coated on colloidal particle (as polymer or inorganic matter) surface, with and preparation method thereof.
For finishing above-mentioned purpose, the invention provides a kind of metal nanoparticles mixture that shows color in the visible range, wherein two or more nano particle is selected from by showing red metal nanoparticle, show yellow metal nanoparticle, with the group that shows that blue metal nanoparticle is formed, these nano particles mix with multiple composition ratio.
In the present invention, the preferred form of metal nanoparticle is: nanosphere, nanometer rods, nanoshell, still also not limited thereto.
In the present invention, show that red metal nanoparticle is a color of spherical gold, show that yellow metal nanoparticle is a Nano silver grain, show that blue metal nanoparticle is gold nanorods, gold nanoshell, gold nano cube or gold nano prism.
Show that red metal nanoparticle is preferably prepared by the following step:
(a) at about 100 ℃ of following backflow HAuCl 4
(b) reducing agent is added in this reflux solution, then heat this mixed solution and make its reaction; With
(c) with the reaction solution cool to room temperature and with its filtration.
Yet, also not limited thereto.
In addition, show that yellow metal nanoparticle is preferably prepared by the following step:
(a) with AgNO 3, PVP (polyvinylpyrrolidone) and EG (ethylene glycol) mix, and stir this final mixture;
(b) at about 120 ℃ these mixtures that reflux down; With
(c) with back flow reaction solution cool to room temperature and with its filtration.
Yet, also not limited thereto.
Equally, show that blue metal nanoparticle is preferably prepared by the following step:
(a) reducing agent is added in the Nano silver grain of the demonstration yellow for preparing as mentioned above, at about 100 ℃ these final mixtures that reflux down;
(b) with HAuCl 4When solution adds this back flow reaction solution to, allow its reaction simultaneously; With
(c) cooled reaction solution is to room temperature and with its filtration.
Yet, also not limited thereto.
In addition, the invention provides the multi-colour metal colloidal particle, wherein metal nanoparticles mixture is coated on colloidal particle (as polymer or the inorganic matter) surface.
Equally, the invention provides the method for preparing the multi-colour metal colloidal particle, show that wherein the metal nanoparticles mixture of color is coated on the colloidal particle surface in the visible range, this method comprises the steps:
(a) metal nanoparticles mixture is mixed with polymer or colloidal inorganic particle and allow its reaction; With
(b) obtain to scribble the multi-colour metal colloidal particle of metal nanoparticle from product.
In the present invention, the surface of polymer or colloidal inorganic particle is preferred handles with the functional group that organizes down, and this is organized by amine, mercaptan, and hydroxyl, carboxyl and amino dextrin group are formed.In addition, preferably from organizing down, this is organized by polystyrene, polystyrene-methacrylic acid, polystyrene-divinylbenzene, polymethyl methacrylate, polyphenylene oxide, polyurethanes, dendritic (dendrimer), silica, silica, TiO for polymer or colloidal inorganic particle 2Form with bead.
According to the present invention, in the method for preparing the multi-colour metal colloidal particle, the reaction of step (a) is preferably carried out under the condition of about pH6.8.
Further feature of the present invention is by will be more readily apparent from following detailed Description Of The Invention and the appending claims.
Description of drawings
Fig. 1 shows the schematic diagram for preparing polychrome colloidal particle method by coating metal nanoparticle mixture on polymer or inorganic grain, and the metal nanoparticle that wherein demonstrates three primary colors (redness, yellow and blue) mixes with certain composition ratio.
Fig. 2 demonstration obtains metal nanoparticles mixture by the metal nanoparticle that goes out three primary colors (redness, yellow and blue) with certain composition ratio mixed display.
Fig. 3 shows the absorption spectrum of metal nanoparticles mixture, wherein show red golden nanometer particle and show that yellow Nano silver grain mixes with the definite composition ratio, and metal nanoparticles mixture demonstrates multiple color.
Fig. 4 shows the absorption spectrum of metal nanoparticles mixture, show that wherein the gold nanoshell particles of yellow Nano silver grain and demonstration blueness is mixed with the definite composition ratio, and metal nanoparticles mixture demonstrates multiple color.
Fig. 5 shows the absorption spectrum of metal nanoparticles mixture, and the gold nanoshell particles of the golden nanometer particle of wherein demonstration redness and demonstration blueness is with the mixing of definite composition ratio, and the metal nanoparticles mixture demonstration removes multiple color.
Fig. 6 shows the pipe contain colloidal particle, and this colloidal particle prepares by respectively the metal nanoparticles mixture of corresponding seven kinds of rainbow colors being coated on the spherical polystyrene particulate.
Fig. 7 is transmission electron microscope (TEM) image on colloidal particle surface, and this colloidal particle is coated on the polymer particle in the solution of four kinds of pH values (pH4.0, pH 6.0, pH 6.8 and pH 8.5) by the golden nanometer particle with sphere and prepares.
Fig. 8 shows the color of colloidal particle, and this colloidal particle is coated on the polymer particle in the solution of four kinds of pH values (pH 4.0, and pH 6.0, pH 6.8 and pH 8.5) by the golden nanometer particle with sphere and prepares.
Fig. 9 is SEM (SEM) image on colloidal particle surface, and this colloidal particle obtains by metal nanoparticles mixture being coated on polymer and the silicon particle surface according to the present invention.
Figure 10 is according to the lip-deep metal nanoparticle TEM of the polymer particle image that is coated on of the present invention.For distinguishing each feature structure, select red color of spherical gold, yellow spherical silver nanoparticles, the spherical silver nanoparticles of green and the mixture and the blue nanoshell type of gold nanoparticles of nanoshell type of gold nanoparticles respectively.In Figure 10, right row's photo is that left bank amplifies 5 times photo.
Figure 11 shows the result who the polymer particles that scribbles spherical silver nanoparticles is carried out energy dispersive X-ray-spectroscopy (EDX) analysis.
Figure 12 is the EDX analysis result that scribbles the polymer particles of spherical silver nanoparticles and nanoshell type of gold nanoparticles.
Figure 13 is the EDX analysis result that scribbles the polymer particles of nanoshell type of gold nanoparticles.
The specific embodiment
The present invention relates to show the metal nanoparticles mixture of color in the visible range, wherein two or more nano particle is selected from by showing red metal nanoparticle, show yellow metal nanoparticle and showing the group that blue metal nanoparticle is formed, these nano particles mix with multiple composition ratio, also relate to the polychrome colloidal particle that metal nanoparticles mixture is coated in polymer or colloidal inorganic particle, and preparation method thereof.
As used herein, " mix " and refer to that the metal nanoparticle that shows two different colours mixes with 0.1: 9.9 to 9.9: 0.1 composition ratio with multiple composition ratio, this will describe in the following embodiments, be presented at the multiple color between above two kinds of colors thus.Therefore, the spectrum that is equivalent to redness-red as fire look-yellow can show by showing that red nano particle mix with the nano particle that shows yellow; The color that is equivalent to yellow-green-blue color spectrum shows by showing that yellow nano particle mixes with the nano particle that shows blueness; Show by showing that blue nano particle mixes with the nano particle that shows redness with the color that is equivalent to blueness-navy blue-pansy-red spectrum.
For showing multiple color, select to show red nano particle, show yellow nano particle and show that blue nano particle is main composition material.Redness is to be shown by the spherical golden nanometer particle of preparation and yellow is to be shown by the Nano silver grain of preparation sphere.Blueness is the gold particle demonstration by the preparation nanoshell type, is used to wherein show that yellow Nano silver grain preparation shows blue hollow type golden nanometer particle.
Can be as showing that redness, yellow and blue metal nanoparticle have polytype and size, except that nanosphere, it comprises nanometer rods, nanoshell, nanocube, nanoprisms body etc.In this case, wherein show redly, these yellow and blue metal nanoparticles mix with suitable composition ratio, can prepare demonstration by red, yellow and blue comprehensive and the metal nanoparticle solution of multiple color.In addition, can be by prepare the spherical particle that shows multiple color with metal nanoparticle solution coat particulate.
If three kinds of metal nanoparticles according to the present invention can demonstrate all colours (Fig. 2) in the visible range with certain composition ratio combination.That is, mix with certain composition ratio with showing yellow spherical silver nanoparticles if wherein show red spherical metal nano particle, the multiple color between redness and yellow can show (Fig. 3).Equally, mix with certain composition ratio with the golden nanometer particle that shows blue nanoshell type if wherein show yellow spherical silver nanoparticles, the multiple color between yellow and blueness can show (Fig. 4).In addition, mix with certain composition ratio with the golden nanometer particle that shows blue nanoshell type if wherein show red color of spherical gold, the multiple color between redness and blueness can show (Fig. 5).Therefore, according to the present invention, whole colors of visible range can show by comprehensive three kinds of metal nanoparticles.
In addition, demonstrate multiple color colloidal particle can by with as mentioned above the preparation metal nanoparticle coated polymeric or metal particle prepare.For example, as shown in Figure 6, demonstrating irised colloidal particle can be by preparing with the ps particle that shows the seven non-ferrous metal nanoparticle mixture coating sphere that is equivalent to the rainbow color.
In the present invention, the polystyrene that its surface is replaced by amido uses as particulate, but not limited thereto.For example, polymer particle, as has a polystyrene of multiple functional group, these functional groups comprise amido, mercapto, hydroxyl, carboxyl, amino dextrin base etc., also have polystyrene-methacrylic acid, polystyrene-divinylbenzene, polymethyl methacrylate, polyphenylene oxide, polyurethanes, dendritic, silica, silica, TiO2, bead etc. can be used as particulate.
Used particle size is not limited to the scope of μ m size among the present invention, can extend to inorganic nano-particle or polymer particle with 100nm-1mm magnitude range.
Embodiment
Following specific embodiment purpose is to illustrate the present invention, but should not be considered to limitation of the present invention.The present invention is by the appended claims range of definition.
In the following example, identical accompanying drawing number is represented similar elements.In addition, multiple element and zone in the accompanying drawing generally illustrate, and it should not be interpreted into qualification the present invention by relative size or interval.
Especially, show certain combination ratio of trichromatic nano particle below among the embodiment, to those skilled in the art, it obviously is not to be confined to this.
Embodiment 1: preparation shows the nanoparticle mixture of multiple color
＜1-1〉the trichromatic metal nanoparticle of preparation demonstration
For preparation shows red, yellow and blue, just trichromatic metal nanoparticle at first prepares color of spherical gold and Nano silver grain.
For preparation shows red color of spherical gold, with the HAuCl of 500ml 4Thereby (1mM) adding round-bottomed flask to heats under 100 ℃ of backflows.The natrium citricum of 50ml (38.8mM) is added in the final solution as reducing agent.After the color of determining reaction solution became kermesinus from yellow, reaction liquid further heated 15 minutes, and cool to room temperature then filters with 0.2 μ m micro-filter then.
For preparation shows yellow Nano silver grain, with AgNO 3(0.04g), PVP (polyvinylpyrrolidone) (1g) and the EG (ethylene glycol) of 7.5ml mix, and stir energetically.This mixture refluxed 4 hours down at 120 ℃, cool to room temperature, and filter with 0.2 μ m micro-filter.
Be the particle of the blue gold nanoshell type of preparation demonstration, use the Nano silver grain of the demonstration yellow of preparation as mentioned above.The Nano silver grain of the demonstration yellow of 1ml refluxed 10 minutes down at 100 ℃ then with 50ml natrium citricum (the 0.4mM aqueous solution) dilution.Stir this final solution energetically and regulate syringe pump injects 2ml with 45ml/ hour speed HAuCl with trace simultaneously 4(10mM), allow further reaction 20 minutes then, follow cool to room temperature, the micro-filter with 0.2 μ m filters then.
＜1-2〉preparation shows the metal nanoparticles mixture of multiple color
Multiple color is by showing that red, yellow and blue hybrid metal nano particle shows, that is, by embodiment＜1-1〉with the three primary colors of certain composition ratio preparation.In this case, by the UV-vis-spectrometry OD (optical density) of used metal nanoparticle is adjusted to 2.8.
At first, show that the yellow Nano silver grain of red color of spherical gold and demonstration mixes with 9: 1,7: 3,5: 5,3: 7,1: 9 volume ratio respectively.Therefore, demonstrate and be equivalent to a kind of color (Fig. 2 and Fig. 3) of crossing over the redness-red as fire look-yellow spectrum in the visible range.
The gold nanoshell particles that shows yellow Nano silver grain and demonstration blueness is mixed with 9: 1,7: 3,5: 5,3: 7,1: 9 volume ratio respectively.Therefore, demonstrate and be equivalent to a kind of color (Fig. 2 and Fig. 4) of crossing over the green-blue color spectrum in the visible range.
Show blue gold nanoshell particles and show that red golden nanometer particle mixes with 9: 1,7: 3,5: 5,3: 7,1: 9 volume ratio respectively.Therefore, demonstrate and be equivalent to a kind of color (Fig. 2 and Fig. 5) of crossing over the blueness-navy blue-pansy-red spectrum in the visible range.
Embodiment 2: preparation scribbles the colloidal particle of the metal nanoparticles mixture that shows multiple color
From by embodiment＜1-2〉select to show seven kinds of metal nanoparticles mixture of seven kinds of colors that are equivalent to the rainbow color the metal nanoparticles mixture of preparation after, selected each metal nanoparticles mixture is applied on the polystyrene bead of handling with amido on the surface.Because coating process, polystyrene bead (3.18 μ m, the Bangs laboratory, the 1wt% aqueous solution) diluted (5X), the dilute solution of 0.5ml mixes with every kind of metal nanoparticles mixture that the demonstration of 4ml is equivalent to seven kinds of colors of rainbow color then, then it is regulated OD (optical density) to 2.8.
Polystyrene bead at room temperature was coated with one day with final mixture.At room temperature 4 hours postprecipitations of polymer particles that confirmation is coated with, and it is easy to separate under the rotating speed of 1000rpm with centrifuge.Therefore, as shown in Figure 6, prepared colloidal particle demonstrates seven kinds of colors.
For finding the optimal pH reaction condition of coating metal nanoparticle mixture on the colloidal particle surface, under a plurality of pH conditions, metallic colloid particle and microparticle surfaces reaction.Fig. 7 is TEM (transmission electron microscope) photo that shows the colloidal particle surface, and this colloidal particle is coated on the polymer particle under four kinds of different pH values (pH 4.0, and pH 6.0, pH 6.8 and pH 8.5) solution by the golden nanometer particle with sphere and prepares.Fig. 8 shown by will be as mentioned above in four kinds of different pH solution color of spherical gold be coated on the color of the colloidal particle for preparing on the polymer particle.
As shown in Figure 7 and Figure 8, in the reaction solution of pH 4, pH 6, pH 6.8 and pH 8.5, to show that respectively red color of spherical gold is coated on the polystyrene nanoparticle surface, the result is if pH is 6.8 or below it, the spherical metal nano particle is coated on the surface of polystyrene bead with a bunch shape (cluster) form, if pH is 6.8 or more than it, each spherical metal nano particle is evenly distributed on the surface of polystyrene bead.Therefore, can observe according to bunch collection (clustering) degree, the color of solution from the redness to the pansy then navy blue changing.Based on experimental result, all are reflected under the condition of pH 6.8 carries out.
Embodiment 3: the identification of polychrome colloidal particle
The colloidal particle that scribbles the multiple color metal nanoparticles mixture of demonstration for preparing in an embodiment can be discerned with SEM (SEM) and TEM (transmission electron microscope).That is, will scribble the polymer particle after separating of the metal nanoparticle of embodiment 2 preparations, its surface texture uses SEM (Fig. 9) to analyze and be coated on the lip-deep structures of metal nanoparticles use TEM of polymer particle (Figure 10) and thoroughly checks.
Fig. 9 is scanning electron microscopy (SEM) photo that shows the colloidal particle surface, and this colloidal particle obtains by metal nanoparticles mixture being coated on polymer and the silica particle surface.For easily distinguishing each feature structure, select to show the color of spherical gold of redness respectively, the spherical silver nanoparticles of displaing yellow show the spherical silver nanoparticles of green and the mixture of nanoshell type of gold nanoparticles, and nanoshell type of gold nanoparticles is showed.
Figure 10 is used to discern the TEM image that is coated on the lip-deep structures of metal nanoparticles of polymer particles.For distinguishing each feature structure, select to show the color of spherical gold of redness respectively, the spherical silver nanoparticles of displaing yellow shows the spherical silver nanoparticles of green and the mixture and the apparent blue nanoshell type of gold nanoparticles of nanoshell type of gold nanoparticles and shows.In Figure 10, right row's photo is that left bank amplifies 5 times photo.
As shown in figure 10, can observe if yellow, then spherical silver nanoparticles is coated on the polymer beads sub-surface; If blue, then the golden nanometer particle of nanoshell type is coated on the surface of polymer particle.Thus shown in second image of Figure 10, because golden nanometer particle has empty inside, so it can be easy to distinguish from spheroidal particle.
Simultaneously, if green, then the golden nanometer particle of spherical silver nanoparticles and nanoshell type is coated with together, thereby because its architectural difference demonstrates green.
In addition, be coated on the lip-deep metal component of polymer particles and can discern (Figure 11 to 13) by EDX (energy dispersive X ray-spectroscopy) analysis.Figure 11 is the polymer particles EDX analysis result that scribbles spherical silver nanoparticles, wherein is easy to identify the component of Nano silver grain.Figure 12 scribbles to show the green spherical silver nanoparticles and the polymer particles EDX analysis result of nanoshell type of gold nanoparticles, therefrom discerns the existence of Nano silver grain and golden nanometer particle easily.That is, can confirm to show that green spheroidal particle contains the nanoshell type of gold nanoparticles that shows that yellow Nano silver grain is blue with demonstration.Equally, Figure 13 is the EDX analysis result that scribbles the polymer particles of nanoshell type of gold nanoparticles, therefrom can discern the existence of golden nanometer particle.
When the present invention is illustrated by means of specific illustrative embodiment, not by embodiment but work the effect of qualification by appending claims.Should be understood that those skilled in the art can change or improve embodiment under the prerequisite that does not deviate from scope of the present invention and aim.
Industrial applicibility
As described in detail above, according to the present invention, the whole colors in the visible range can show by the trichromatic metal nanoparticle of mixed display suitably. And according to the present invention, show that the polychrome colloidal particle of multiple color can be by preparing with the metal nanoparticles mixture coated polymeric or the colloidal inorganic particle that show multiple color. Biology sensor or its analog that can be used as biological and medical field by the colloidal particle with the metal nanoparticles mixture coated polymeric that shows multiple color or the demonstration multiple color that inorganic particles prepares.

Claims (14)

1. metal nanoparticles mixture that shows color in the visible range, it is characterized in that, two or more nano particle is selected from by showing red metal nanoparticle, show yellow metal nanoparticle and showing the group that blue metal nanoparticle is formed, and these nano particles mix with multiple composition ratio.
2. metal nanoparticles mixture as claimed in claim 1 is characterized in that, the form of metal nanoparticle can be selected from the group of being made up of nanosphere, nanometer rods, nanoshell, nanocube and nanoprisms body.
3. metal nanoparticles mixture as claimed in claim 1, it is characterized in that, show that red metal nanoparticle is a color of spherical gold, show that yellow metal nanoparticle is a Nano silver grain, show that blue metal nanoparticle is to be selected from the group of being made up of gold nanorods, gold nanoshell, gold nano cube and gold nano prism.
4. metal nanoparticles mixture as claimed in claim 1 is characterized in that, shows that red metal nanoparticle is prepared by the following step:
(a) at about 100 ℃ of following backflow HAuCl 4
(b) reducing agent is added in this reflux solution, then heat this mixed solution and make its reaction; With
(c) with the reaction solution cool to room temperature and with its filtration.
5. metal nanoparticles mixture as claimed in claim 1 is characterized in that, shows that yellow metal nanoparticle is prepared by the following step:
(a) with AgNO 3, polyvinylpyrrolidone and ethylene glycol mixes, and stirs this final mixture;
(b) at about 120 ℃ these mixtures that reflux down; With
(c) with the reaction solution cool to room temperature of backflow and with its filtration.
6. metal nanoparticles mixture as claimed in claim 1 is characterized in that, shows that blue metal nanoparticle is prepared by the following step:
(a) reducing agent is added to according in the yellow Nano silver grain of the demonstration of claim 5 preparation, and at about 100 ℃ these final mixtures that reflux down;
(b) when with HAuCl 4Solution carries out this reaction when adding this back flow reaction solution to; With
(c) cooled reaction solution is to room temperature and with its filtration.
7. the multi-colour metal colloidal particle is characterized in that, polymer or colloidal inorganic particle are coated with each metal nanoparticles mixture of with good grounds claim 1～6.
8. multi-colour metal colloidal particle as claimed in claim 7 is characterized in that, the surface of polymer or colloidal inorganic particle is preferred handles with the functional group that is selected from down group, and this group is made up of amido, mercapto, hydroxyl, carboxyl and amino dextrin base.
9. multi-colour metal colloidal particle as claimed in claim 7, it is characterized in that, polymer or colloidal inorganic particle are selected from down group, and this is organized by polystyrene, polystyrene-methacrylic acid, polystyrene-divinylbenzene, polymethyl methacrylate, polyphenylene oxide, polyurethanes, dendritic, silica, silica, TiO 2Form with bead.
10. multi-colour metal colloidal particle as claimed in claim 7 is characterized in that, the size of polymer or colloidal inorganic particle is 100nm～1mm.
11. a method that is used to prepare the multi-colour metal colloidal particle is characterized in that, the metal nanoparticles mixture of color is coated on the colloidal particle surface in showing the visible range, and this method comprises the steps:
(a) each metal nanoparticles mixture of claim 1～6 is mixed with polymer or colloidal inorganic particle and allow its reaction; With
(b) obtain to scribble the multi-colour metal colloidal particle of metal nanoparticle from end product.
12. preparation multi-colour metal colloidal particle method as claimed in claim 11 is characterized in that, step (a) is about at pH under 6.8 the condition carries out.
13. the method for preparing the multi-colour metal colloidal particle as claimed in claim 11 is characterized in that, handle with the functional group that organizes down on the surface of polymer or colloidal inorganic particle, and this group is made up of amido, mercapto, hydroxyl, carboxyl and amino dextrin base.
14. as preparing the method for multi-colour metal colloidal particle as described in the claim 11, it is characterized in that, polymer or colloidal inorganic particle are selected from down group, and this group is by polystyrene, polystyrene-methacrylic acid, polystyrene-divinylbenzene, poly-methyl-acrylate, polyphenylene oxide, polyurethanes, dendritic, silica, silica, TiO 2Form with bead.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108884331A (en) * 2016-03-30 2018-11-23 诺利塔克股份有限公司 The red pigment of ceramic decoration
WO2024078328A1 (en) * 2022-10-14 2024-04-18 江苏集萃智能液晶科技有限公司 Multi-color dimming device and application thereof

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8033715B2 (en) * 2007-11-08 2011-10-11 Illinois Institute Of Technology Nanoparticle based thermal history indicators
JP2009221140A (en) * 2008-03-14 2009-10-01 National Institute Of Advanced Industrial & Technology Colored nanoparticles for cosmetic and its manufacturing method
JP5456651B2 (en) * 2010-01-07 2014-04-02 八千代工業株式会社 Metal colloid, its production method and its application
US9193879B2 (en) 2010-02-17 2015-11-24 Baker Hughes Incorporated Nano-coatings for articles
CH702835A2 (en) * 2010-03-11 2011-09-15 Neollia Sas colored solid precious material formed by assembly of noble metal nanoparticles.
US8318838B2 (en) * 2010-09-09 2012-11-27 Baker Hughes Incorporated Method of forming polymer nanocomposite
US8314177B2 (en) 2010-09-09 2012-11-20 Baker Hughes Incorporated Polymer nanocomposite
JP5358648B2 (en) * 2010-11-05 2013-12-04 田中貴金属工業株式会社 Blue gold nanoparticles for immunological measurement, production method thereof and measurement method using the same
PL2714419T3 (en) * 2011-06-02 2015-12-31 Fabrica Nac De Moneda Y Timbre Real Casa De La Moneda Use of raman markers for authenticating security documents
US9040013B2 (en) 2011-08-04 2015-05-26 Baker Hughes Incorporated Method of preparing functionalized graphene
US9428383B2 (en) 2011-08-19 2016-08-30 Baker Hughes Incorporated Amphiphilic nanoparticle, composition comprising same and method of controlling oil spill using amphiphilic nanoparticle
US9441462B2 (en) 2012-01-11 2016-09-13 Baker Hughes Incorporated Nanocomposites for absorption tunable sandscreens
ES2688381T3 (en) * 2012-09-28 2018-11-02 Stelo Technologies Methods for making silver nanoparticles and their applications
CN103143724B (en) * 2013-03-16 2015-04-22 安徽工业大学 Preparation method of nanometer silver colloid in different shapes
CN103163095A (en) * 2013-03-25 2013-06-19 江南大学 Visual multifunctional detection method based on nano-silver
CN106415196B (en) * 2014-04-04 2020-03-24 加州大学评议会 Colorimetric stress memory sensor based on plasmon nanoparticles
JP6536931B2 (en) * 2014-11-18 2019-07-03 公立大学法人兵庫県立大学 Surface enhanced Raman measuring method and surface enhanced Raman measuring apparatus
BR112019012999A2 (en) 2016-12-21 2019-12-10 Nanobiotix coated nanoparticles for use to modulate electrical polarization of neurons
CA3047649A1 (en) 2016-12-21 2018-06-28 Nanobiotix Nanoparticles for use for treating a neuronal disorder
CA3047651A1 (en) * 2016-12-21 2018-06-28 Nanobiotix Nanoparticles for use for enhancing brain performances or for treating stress
CN111036936A (en) * 2019-12-21 2020-04-21 浙江加州国际纳米技术研究院台州分院 Method for improving yield of silver nanoparticles synthesized by polyol method
CN111112639B (en) * 2020-01-02 2023-04-07 西安工业大学 Nanoscale spherical silver particles with room-temperature antifriction effect and preparation method thereof
CN114835868B (en) * 2022-04-06 2024-01-09 合肥工业大学 Preparation method of self-repairable and recyclable polymer nano composite film

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1198556A (en) * 1982-05-14 1985-12-31 Martyn C. Barker Compositions comprising inorganic particles
US6025202A (en) * 1995-02-09 2000-02-15 The Penn State Research Foundation Self-assembled metal colloid monolayers and detection methods therewith
KR100379250B1 (en) * 2000-12-04 2003-04-08 한국과학기술연구원 Composite Polymers Containing Nanometer-sized Metal Particles and Fabrication Method Thereof
KR100379248B1 (en) * 2000-12-04 2003-04-08 한국과학기술연구원 Inorganic-organic hybrid polymers composed of nano-particles on the surface using dendrimers and Fabrication Method Thereof
CA2444705A1 (en) * 2001-04-19 2002-10-31 Commonwealth Scientific And Industrial Research Organisation Coating composition capable of absorbing uv radiation
CA2445877C (en) * 2001-04-30 2006-12-19 Postech Foundation Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof
US20030215638A1 (en) * 2001-11-05 2003-11-20 Wm. Marsh Rice University Reduced symmetry nanoparticles
US7129519B2 (en) * 2002-05-08 2006-10-31 Advanced Technology Materials, Inc. Monitoring system comprising infrared thermopile detector
US20050287680A1 (en) * 2004-06-25 2005-12-29 Srivatsa Venkatasubbarao Multianalyte assay method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US11130872B2 (en) 2016-03-30 2021-09-28 Noritake Co., Limited Red paint for ceramic decoration
US11674043B2 (en) 2016-03-30 2023-06-13 Noritake Co., Limi Ted Red paint for ceramic decoration
WO2024078328A1 (en) * 2022-10-14 2024-04-18 江苏集萃智能液晶科技有限公司 Multi-color dimming device and application thereof

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